WO2009036901A1 - Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'imines - Google Patents

Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'imines Download PDF

Info

Publication number
WO2009036901A1
WO2009036901A1 PCT/EP2008/007272 EP2008007272W WO2009036901A1 WO 2009036901 A1 WO2009036901 A1 WO 2009036901A1 EP 2008007272 W EP2008007272 W EP 2008007272W WO 2009036901 A1 WO2009036901 A1 WO 2009036901A1
Authority
WO
WIPO (PCT)
Prior art keywords
pyrid
chlorine
optionally substituted
general formula
fluorine
Prior art date
Application number
PCT/EP2008/007272
Other languages
German (de)
English (en)
Inventor
Norbert Lui
Jens-Dietmar Heinrich
Original Assignee
Bayer Cropscience Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Cropscience Ag filed Critical Bayer Cropscience Ag
Priority to CN200880107472XA priority Critical patent/CN101835754B/zh
Priority to MX2010002453A priority patent/MX2010002453A/es
Priority to KR1020107008224A priority patent/KR101520337B1/ko
Priority to US12/677,951 priority patent/US8324393B2/en
Priority to EP08801866.8A priority patent/EP2200984B1/fr
Priority to DK08801866.8T priority patent/DK2200984T3/en
Priority to JP2010525231A priority patent/JP5295248B2/ja
Priority to BRPI0816868A priority patent/BRPI0816868B1/pt
Priority to ES08801866.8T priority patent/ES2445653T3/es
Publication of WO2009036901A1 publication Critical patent/WO2009036901A1/fr
Priority to IL204000A priority patent/IL204000A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to a process for the preparation of 2,2-difluoroethanamine derivatives starting from 2,2-difluoroethylimine derivatives.
  • Another object of the present invention are used in this process according to the invention as starting compounds 2,2-difluoroethylimine derivatives, their preparation and their use for the preparation of 2,2-difluoroethylamine derivatives.
  • 2,2-difluoroethylamines are important intermediates for the production of agrochemical active ingredients.
  • Corresponding 2,2-difluoroethylamine derivatives can be used, for example, in the synthesis of insecticidally active enaminocarbonyl compounds, for example 4-aminobut-2-enolide compounds.
  • Enaminocarbonyl compounds which comprise 2,2-difluoroethylamino building blocks are known, for example, from international patent applications WO 2007/1 15644 and WO 2007/1 15646.
  • WO 2007/1 15644 discloses that 2,2-difluoroethylamine derivatives, for example the compound of the below formula (IIIa), are obtained by alkylating the amine of the formula (Ia) with optionally substituted chloromethylpyridine of the formula (IIa) see Scheme 1 of DE 10 2006 015 467 A, see preparation of starting compounds, compounds of formula (III), IH-I: N - [(6-chloropyridin-3-yl) methyl] -2,2-difluoroethyl-1 amine).
  • a disadvantage of this process is the low yield of 53%, which is due to the possible multiple alkylation of the nitrogen atom. This proportion of multiple alkylation can only be reduced by using a large excess of amine, but this is uneconomical for a costly amine.
  • 2,2-difluoroethylamine derivatives which is preferably simple and inexpensive to perform.
  • the 2,2-difluoroethylamine derivatives obtainable by this desired process should preferably be obtained in high yield and high purity.
  • the desired process is to preserve the desired target compounds without the need for complex purification methods.
  • This object is achieved by a process for the preparation of 2,2-difluoroethylamine derivatives.
  • the desired 2,2-difluoroethylamine derivatives of the general formula (III) are prepared by hydrogenation of the corresponding 2,2-difluoroethylimine derivatives of the general formula (IV).
  • the desired 2,2-difluoroethylamine derivatives of the general formula (III) are obtained in good yields in high purity under the preferred reaction conditions according to the invention and specified below, with which the process according to the invention overcomes the abovementioned disadvantages.
  • the desired compounds are obtained in a purity which does not require extensive work-up of the immediate reaction product in general. Compared to the process known from the prior art, which starts from an amine to be alkylated according to Scheme 1, the yields can be improved by the inventive method.
  • the purity of the desired target compound achieved by the process according to the invention is greater since no multiple alkylation takes place.
  • a derivative is taken to mean a substance of similar structure derived from the designated organic backbone (building block), ie a 2,2-difluoroethylamine derivative is understood, for example, to mean a compound comprising a 2,2-difluoroethylamine building block , ID the above-mentioned general formula (HD and (TV), the radical A has the following meaning:
  • pyrid-2-yl or pyrid-4-yl or pyrid-3-yl which is optionally substituted in the 6-position by fluorine, chlorine, bromine, methyl, trifluoromethyl or trifluoromethoxy or pyridazin-3-yl, which optionally substituted in the 6-position by chlorine or methyl or for pyrazine-3-yl or 2-chloro-pyrazine-5-yl or l, 3-thiazol-5-yl which is optionally substituted in the 2-position Chlorine or methyl, or
  • X is halogen, alkyl or haloalkyl
  • Y is halogen, alkyl, haloalkyl, haloalkoxy, azido or cyano.
  • A is preferably selected from the group consisting of 6-fluoropyrid-3-yl, 6-chloropyrid-3-yl, 6-bromo-pyrid-3-yl, 6-methyl-pyrid-3-yl, 6-trifluoromethylpyrid-3-yl, 6-trifluoromethoxypyrid-3-yl, 6-chloro-1, 4-pyridazin-3-yl, 6-methyl-1,4-pyridazin-3-yl, 2-chloro l, 3-thiazol-5-yl or 2-methyl-l, 3-thiazol-5-yl, 2-chloro-pyrimidin-5-yl, 2
  • A is more preferably selected from the group consisting of 6-fluoro-pyrid-3-yl, 6-chloro-pyrid-3-yl, 6-bromopyrid-3-yl, 6-chloro-1, 4-pyridazine-3 -yl, 2-chloro-1, 3-thiazol-5-yl, 2-chloro-pyrimidin-5-yl, 5-fluoro-6-chloro-pyrid-3-yl, 5,6-dichloro-pyrid-3 -yl, 5-bromo-6-c-chloropyrid-3-yl, 5-fluoro-6-bromo> pyrid-3-yl, 5-chloro-6-bromo-pyrid-3-yl, 5, ⁇ -dibromo-pyrid-3-yl, 5-methyl-6-chloro-pyrid-3-yl, 5-chloro-6-iodo-pyrid-3-yl and 5-difluoromethyl-6-chloro-
  • A is very particularly preferably selected from the group consisting of 6-chloropyrid-3-yl, 6-bromo-pyrid-3-yl, 6-chloro-1, 4-pyridazin-3-yl, 2-chloro 1, 3-thiazol-5-yl, 5-fluoro-6-chloro-pyrid-3-yl and 5-fluoro-6-bromo-pyrid-3-yl.
  • alkyl either alone or in combination with other terms such as, for example, haloalkyl, means a radical of a saturated, aliphatic hydrocarbon group having 1 to 12 carbon atoms, which may be branched or unbranched for C 1 -C 12 -alkyl radicals, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert Pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, hexyl n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, of these al
  • aryl is understood according to the invention to mean an aromatic radical having 6 to 14 carbon atoms, preferably phenyl.
  • arylalkyl is understood to mean a combination of radicals "aryl” and “alkyl” defined according to the invention, the radical generally being bound via the alkyl group, examples of which are benzyl, phenylethyl or .alpha.-methylbenzyl, benzyl being particularly preferred.
  • halogen-substituted radicals for example haloalkyl
  • halogenated radicals are halogenated one or more times up to the maximum possible number of substituents
  • Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • alkoxy either alone or in combination with other terms, such as, for example, haloalkoxy, is understood herein to mean a radical O-alkyl, the term “alkyl” having the meaning given above.
  • Optionally substituted radicals may be monosubstituted or polysubstituted, wherein in a multiple substitution, the substituents may be the same or different.
  • Complex hydrides are generally understood as meaning charged metal complexes containing at least one hydride ligand. Examples thereof are lithium aluminum hydride (LiAlH 4 ), LiAlH (O-tert-butyl) 3> LiAlH (O-methyl) 3) NaAlEt 2 H 2 , sodium borohydride (NaBH 4 ) and the like. Examples of non-complex metal and metalloid hydrides are AlH 3 , DIBAL-H (AlH (isobutyl) 2 ) and the like. Of these, the use of sodium borohydride (NaBH 4 ) is particularly preferred.
  • the reaction with the complex metal hydrides or complex metal hydrides or semimetal hydrides not the can in a vacuum, at atmospheric pressure or under excess pressure and at temperatures of -30 to 150 ° C, preferably -10 to 60 0 C is performed.
  • any hydrogenation catalyst can be used as the catalyst.
  • Suitable catalysts optionally contain one or more metals of Groups 8-10 of the Periodic Table on any conventional inorganic carrier.
  • noble metal catalysts such as ruthenium catalysts, palladium catalysts,
  • Platinum catalysts and rhodium catalysts, Raney nickel catalysts and Lindlar catalysts can also hydrogenations homogeneous catalysts, for example on the Wilkinson catalyst.
  • the corresponding catalysts may also be used in supported form, for example on carbon (carbon or activated carbon), alumina, silica, zirconia or titania.
  • Corresponding catalysts are known per se to the person skilled in the art. Especially preferred are Raney nickel catalysts.
  • the catalytic hydrogenation can be carried out under pressure in an autoclave or at atmospheric pressure in a hydrogen gas atmosphere.
  • the hydrogen gas atmosphere may additionally contain inert gases, for example argon or nitrogen.
  • the catalytic hydrogenation is preferably carried out at a Ternperaiui of 10 to 60 0 C, more preferably at 20 to 40 0 C.
  • the hydrogen pressure is usually 0.1 to 50 bar, preferably 0.1 to 30 bar.
  • solvents are advantageously used in an amount such that the reaction mixture remains readily stirrable throughout the reduction process.
  • Suitable solvents for carrying out the process according to the invention are all organic solvents which are inert under the reaction conditions, the type of solvent used being of the nature of the reduction procedure, i. in particular on the nature of the reducing agent depends.
  • halogenated hydrocarbons especially chlorinated hydrocarbons such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols such as methanol, ethanol, isopropanol, butanol; Ethers, such as ethyl propyl ether, methyl tert-butyl ether, butyl ether, anisole, phenetole, cyclohexyl methyl ether, dimethyl ether, diethyl ether, dimethyl glycol, diphenyl ether, dihalogenated
  • alcohols especially methanol and ethanol, especially methanol, are preferred.
  • the amounts of solvent used in the reaction according to the invention can be varied within a wide range.
  • amounts of solvent in the range from 1 times to 50 times the amount of solvent, more preferably from 2 times to 40 times the amount of solvent, in particular from 2 times to 30 times the amount of solvent, in each case based on the used 2.2 -Difluorethylimin the general formula (IV) used.
  • NaBH 4 sodium borohydride
  • alcohols especially methanol
  • the reaction according to the invention can be carried out with this system of sodium borohydride (NaBH 4 ) and methanol in particular as follows:
  • the imine is introduced into the alcohol and the sodium borohydride is added in portions in cooling.
  • the mixture is then stirred at a temperature of 30 to 50 0 C and then about 1 to 3 equivalents of water, based on the amount of alcohol added. It is then extracted in the usual way with an organic solvent.
  • the hydrogenation is generally carried out under such reaction conditions (pressure, temperature, stoichiometry, etc.), under which the imine group is hydrogenated to a saturated group, but at the same time the remaining functional groups present in the molecule remain unchanged.
  • the workup (purification) and isolation of the hydrogenated imines can be carried out, for example, by crystallization and / or distillation.
  • the present invention further relates to the use of the compounds of general formula (IV) for the preparation of compounds of general formula (UI) as disclosed in the process described above.
  • the compounds of the general formula (IV) required for the reaction according to the invention can be obtained by reacting aldehydes of the general formula (VI)
  • aldehydes of the formula (II) are commercially available or can be prepared by processes known from the literature (cf., for example, 6-methyl-nicotinaldehyde: EP 0 104 876 A2; 2-chloro-pyrazine-5-carboxaldehyde: DE 3314196 A1).
  • an acid may be added as a catalyst to the reaction to obtain the compounds of the general formula (IV).
  • examples of these are acetic acid, p-toluenesulfonic acid, trifluoroacetic acid.
  • Acetic acid is preferably used.
  • catalysts are used, their amount can be from 0.01 to 10% by weight, based on the 2,2-difluoroethylamine used.
  • the 2,2-difluoroethylamine is used in the form of a salt.
  • a salt is the addition of Lewis acid.
  • suitable salts are the hydrochloride, the acetate or the sulfate.
  • the reaction for the preparation of the compounds of the general formula (IV) can moreover also be carried out so that the water formed in the reaction between amine and aldehyde by condensation is removed from the reaction mixture. This is possible for example by using water-binding agents, for example sodium sulfate, magnesium sulfate or molecular sieve, or by using a device for water separation.
  • the reaction for the preparation of the compounds of the general formula (IV) can generally be carried out in vacuo, at atmospheric pressure or under excess pressure.
  • the temperatures used may also vary depending on the substrates used and are readily apparent to those skilled in the art through routine experimentation.
  • the reaction for the preparation of the compounds of general formula (IV) at a temperature of -20 to 200 0 C, preferably 10 to 100 0 C, are performed.
  • the reaction is carried out at atmospheric pressure and temperatures of 10 to 100 0 C.
  • the reaction for the preparation of the imines of the general formula (IV) can moreover also be carried out in the presence of solvents (diluents).
  • solvents are also used in this process step, preferably in such an amount that the
  • Difluoroethylimine derivatives of the general formula (IV) are all suitable organic solvents under the reaction conditions.
  • halogenated hydrocarbons in particular chlorohydrocarbons, such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, fluorobenzene, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols such as methanol, ethanol, isopropanol, butanol; Ethers, such as ethyl propyl ether, methyl tert-butyl ether, -w-butyl ether, anisole, phenetole, cyclohexyl methyl ether, dimethyl ether, diethyl ether,
  • reaction between amine and aldehyde can also be carried out in bulk.
  • the solvent may be removed by distillation after the end of the reaction. This can be done under normal pressure or reduced pressure at room temperature or elevated temperatures. However, the mixture can also be converted directly into the hydrogenation, which is particularly advantageous for economic reasons.
  • a work-up of the 2,2-difluoroethylimine derivative is then dispensed with.
  • the present invention furthermore relates to the compounds of the general formula (IV) which are used as intermediates in the preparation of the target compounds of the general formula (III):
  • the substituent A generally has the following meaning:
  • X is halogen, alkyl or haloalkyl
  • Y is halogen, alkyl, haloalkyl, haloalkoxy, azido or cyano.
  • A is preferably selected from the group consisting of 6-fluoropyrid-3-yl, 6-chloropyrid-3-yl, 6-bromo-pyrid-3-yl, 6-methyl-pyrid-3-yl, 6-trifluoromethylpyrid-3-yl, 6-trifluoromethoxypyrid-3-yl, 6-chloro-1, 4-pyridazin-3-yl, 6-methyl-1,4-pyridazin-3-yl, 2-chloro l, 3-thiazol-5-yl or 2-methyl-l, 3-thiazol-5-yl, 2-chloro-pyrimidin-5-yl, 2-trifluoromethyl-pyrimidin-5-yl, 5,6-difluoro- pyrid-3-yl, 5-chloro-6-fluoro-pyrid-3-yl, 5-bromo-6-fluoro-pyrid-3-yl, 5-iodo-6-fluoro-pyrid-3-yl, 5- Fluor
  • A is more preferably selected from the group consisting of 6-fluoro-pyrid-3-yl, 6-chloro-pyrid-3-yl, 6-bromopyrid-3-yl, 6-chloro-1, 4-pyridazine-3 -yl, 2-chloro-1,3-thiazol-5-yl, 2-chloro-pyrimidin-5-yl, 5-fluoro-6-chloro-pyrid-3-yl, 5,6-dichloro-pyrid-3-yl, 5-bromo-6-chloro-pyrid-3-yl, 5-fluoro-6-bromo-pyrid-3-yl, 5-chloro-6-bromo-pyrid-3-yl, 5,6-dibromo-pyrid-3-yl, 5-methyl-6-chloro-pyrid 3-yl, 5-chloro-6-iodo-pyrid-3-yl and 5-difluoromethyl-6-chloro-pyrid-3
  • A is very particularly preferably selected from the group consisting of 6-chloropyrid-3-yl, 6-bromo-pyrid-3-yl, 6-chloro-1, 4-pyridazin-3-yl, 2-chloro 1, 3-thiazol-5-yl, 5-fluoro-6-chloro-pyrid-3-yl and 5-fluoro-6-bromo-pyrid-3-yl.
  • the compounds of the general formula (IV) can be used as starting material for the preparation of the 2,2-difluoroethylamine derivatives of the general formula (Iü).
  • insecticidally active enaminocarbonyl compounds which comprise 2,2-difluoroethylamine units and are described, for example, in the international patent applications WO 2007/1 15644 and WO 2007/1 15646 , getting produced.
  • alkenylated at the secondary amine nitrogen for example, by reaction with tetronic acid or derivatives thereof.
  • a corresponding reaction is described in more detail in Scheme I of DE 10 2006 015 467 and leads directly to the insecticidally active enaminocarbonyl compounds.

Abstract

La présente invention concerne un procédé de préparation de dérivés de 2,2-difluoréthylamine, des composés de formule générale (IV) étant réduits en dérivés de 2,2-difluoréthylamine correspondants de formule (III), le radical A ayant la signification indiquée dans la description.
PCT/EP2008/007272 2007-09-18 2008-09-05 Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'imines WO2009036901A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
CN200880107472XA CN101835754B (zh) 2007-09-18 2008-09-05 通过亚胺氢化制备2,2-二氟乙胺衍生物的方法
MX2010002453A MX2010002453A (es) 2007-09-18 2008-09-05 Procedimiento para la preparacion de derivados de 2,2-difluoroetilamina mediante hidrogenacion de imina.
KR1020107008224A KR101520337B1 (ko) 2007-09-18 2008-09-05 이민 수소화에 의한 2,2-디플루오로에틸아민 유도체의 제조방법
US12/677,951 US8324393B2 (en) 2007-09-18 2008-09-05 Method for producing 2,2-difluoroethylamine derivatives by imine hydrogenation
EP08801866.8A EP2200984B1 (fr) 2007-09-18 2008-09-05 Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'imines
DK08801866.8T DK2200984T3 (en) 2007-09-18 2008-09-05 Process for the preparation of 2,2-difluorethylamin derivatives by iminhydrering.
JP2010525231A JP5295248B2 (ja) 2007-09-18 2008-09-05 イミン水素化により２，２−ジフルオロエチルアミン誘導体を製造する方法
BRPI0816868A BRPI0816868B1 (pt) 2007-09-18 2008-09-05 processo para a preparação de derivados de 2,2-difluoroetilamina, intermediários, seu uso e seu processo de preparação
ES08801866.8T ES2445653T3 (es) 2007-09-18 2008-09-05 Procedimiento para la preparación de derivados de 2,2-difluoroetilamina mediante hidrogenación de imina
IL204000A IL204000A (en) 2007-09-18 2010-02-17 METHOD OF CREATING HISTORY 2, 2 - RELIABLE ETHYL DIPLURO THROUGH EIMIN FUNDING

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07116641A EP2039684A1 (fr) 2007-09-18 2007-09-18 Procédé destiné à la fabrication de dérivés de 2,2-difluoréthylamine par hydrogénisation d'imine
EP07116641.7 2007-09-18

Publications (1)

Publication Number Publication Date
WO2009036901A1 true WO2009036901A1 (fr) 2009-03-26

Family

ID=38983732

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/007272 WO2009036901A1 (fr) 2007-09-18 2008-09-05 Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'imines

Country Status (12)

Country Link
US (1) US8324393B2 (fr)
EP (2) EP2039684A1 (fr)
JP (1) JP5295248B2 (fr)
KR (1) KR101520337B1 (fr)
CN (1) CN101835754B (fr)
BR (1) BRPI0816868B1 (fr)
DK (1) DK2200984T3 (fr)
ES (1) ES2445653T3 (fr)
IL (1) IL204000A (fr)
MX (1) MX2010002453A (fr)
TW (1) TWI402245B (fr)
WO (1) WO2009036901A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010105747A1 (fr) 2009-03-16 2010-09-23 Bayer Cropscience Ag Procédé de préparation de dérivés de 2,2-difluoroéthylamine par une hydrogénation des imines
WO2011157650A1 (fr) 2010-06-15 2011-12-22 Bayer Cropscience Ag Procédé de production de dérivés de 2,2-difluoro-éthylamine par alkylation avec des 2,2-difluoro-1-halogénoéthanes
WO2012062702A1 (fr) 2010-11-12 2012-05-18 Bayer Cropscience Ag Procédé de production de 2,2-difluoro-éthylamine à partir d'un composé benzylamine
WO2012062703A1 (fr) * 2010-11-12 2012-05-18 Bayer Cropscience Ag Procédé de production de 2,2-difluoro-éthylamine à partir de prop-2-èn-1-amine
WO2012062740A1 (fr) 2010-11-12 2012-05-18 Bayer Cropscience Ag Procédé de production de dérivés de 2,2-difluoro-éthylamine à partir de n-(2,2-difluoro-éthyl)prop-2-èn-1-amine
WO2012101044A1 (fr) * 2011-01-24 2012-08-02 Bayer Cropscience Ag Procédé de préparation de 2,2-difluoroéthylamine à partir de 2,2-difluoro-1-chloroéthane
WO2014001245A1 (fr) 2012-06-29 2014-01-03 Bayer Cropscience Ag Procédé de production de dérivés de 2,2-difluoroéthylamine par alkylation de 2,2-difluoroéthylamine
US9890120B2 (en) 2014-03-21 2018-02-13 Bayer Cropscience Aktiengesellschaft Preparation of N-[(6-chloropyridin-3-yl)methyl]-2,2-difluoroethan-1-amine by alkylation of 2,2-difluoroethylamine

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX348074B (es) * 2012-04-26 2017-05-25 Bayer Cropscience Ag Procedimiento para preparar n-(5-cloro-2-isopropilbencil) ciclopropanamina.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004047922A1 (de) * 2004-10-01 2006-04-06 Bayer Cropscience Ag Wirkstoffe für die Saatgutbehandlung
DE102006015467A1 (de) * 2006-03-31 2007-10-04 Bayer Cropscience Ag Substituierte Enaminocarbonylverbindungen
WO2008009360A2 (fr) * 2006-07-20 2008-01-24 Bayer Cropscience Ag Dérivés de n'-cyano-n-halogènalkyle-imidamide

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2476644A1 (fr) * 1980-02-21 1981-08-28 Sarget Lab Orthoarylydeneaminophenethylamine, leur preparation et leur utilisation therapeutique
DE3314196A1 (de) 1982-07-16 1983-09-29 CIBA-GEIGY AG, 4002 Basel Heterocyclylaether
NZ205525A (en) 1982-09-29 1985-12-13 Ici Australia Ltd 5-(pyridyl)-cyclohexene-1,3-dione derivatives and herbicidal compositions
HU214992B (hu) * 1989-10-06 1998-12-28 Nippon Soda Co. Ltd. Eljárás aminszármazékok előállítására és ilyen vegyületeket tartalmazó inszekticid készítmények
EP0539588A1 (fr) * 1990-07-05 1993-05-05 Nippon Soda Co., Ltd. Derive d'amine
JP3149989B2 (ja) * 1992-04-28 2001-03-26 広栄化学工業株式会社 ２−クロロ−５−置換アミノメチルピリジン類の製法
JPH0616636A (ja) * 1992-06-30 1994-01-25 Ishihara Sangyo Kaisha Ltd ６−クロロ−３−ピリジルメチルアミン類の製造方法
DE4308395A1 (de) * 1993-03-17 1994-09-22 Basf Ag Verfahren zur Bekämpfung von Schädlingen
JPH08245526A (ja) * 1995-03-10 1996-09-24 Sumitomo Chem Co Ltd 光学活性なアミン類、光学活性なイミン類およびそれらの製造法
DE10221121A1 (de) * 2002-05-13 2003-12-04 Bayer Cropscience Ag N'-Cyano-N-methyl-imidamid-Derivate
EP1789379B1 (fr) * 2004-08-04 2016-10-05 Merck Sharp & Dohme Corp. Procédé diastéréosélectif d'amination réductrice
JP2007284352A (ja) 2004-08-05 2007-11-01 Dai Ichi Seiyaku Co Ltd ピラゾール誘導体
DE102006015468A1 (de) 2006-03-31 2007-10-04 Bayer Cropscience Ag Substituierte Enaminocarbonylverbindungen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004047922A1 (de) * 2004-10-01 2006-04-06 Bayer Cropscience Ag Wirkstoffe für die Saatgutbehandlung
DE102006015467A1 (de) * 2006-03-31 2007-10-04 Bayer Cropscience Ag Substituierte Enaminocarbonylverbindungen
WO2008009360A2 (fr) * 2006-07-20 2008-01-24 Bayer Cropscience Ag Dérivés de n'-cyano-n-halogènalkyle-imidamide

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110127750A (ko) * 2009-03-16 2011-11-25 바이엘 크롭사이언스 아게 이민 수소화에 의한 2,2-다이플루오로에틸아민 유도체의 제조방법
KR101672721B1 (ko) 2009-03-16 2016-11-04 바이엘 인텔렉쳐 프로퍼티 게엠베하 이민 수소화에 의한 2,2-다이플루오로에틸아민 유도체의 제조방법
US8637673B2 (en) 2009-03-16 2014-01-28 Bayer Cropscience Ag Method for producing 2,2-difluoroethylamine derivatives by imine hydrogenation
WO2010105747A1 (fr) 2009-03-16 2010-09-23 Bayer Cropscience Ag Procédé de préparation de dérivés de 2,2-difluoroéthylamine par une hydrogénation des imines
JP2013530171A (ja) * 2010-06-15 2013-07-25 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー ２，２−ジフルオロエチル−１−ハロエタン類を用いてアルキル化することによる２，２−ジフルオロエチルアミン誘導体の調製方法
WO2011157650A1 (fr) 2010-06-15 2011-12-22 Bayer Cropscience Ag Procédé de production de dérivés de 2,2-difluoro-éthylamine par alkylation avec des 2,2-difluoro-1-halogénoéthanes
KR101790159B1 (ko) 2010-06-15 2017-10-25 바이엘 인텔렉쳐 프로퍼티 게엠베하 2,2-디플루오로-1-할로에탄의 알킬화에 의한 2,2-디플루오로에틸아민 유도체의 제조 방법
CN103313969A (zh) * 2010-11-12 2013-09-18 拜耳知识产权有限责任公司 用于由n-(2，2-二氟乙基)丙-2-烯-1-胺起始制备2，2-二氟乙基胺衍生物的方法
WO2012062740A1 (fr) 2010-11-12 2012-05-18 Bayer Cropscience Ag Procédé de production de dérivés de 2,2-difluoro-éthylamine à partir de n-(2,2-difluoro-éthyl)prop-2-èn-1-amine
US8450528B2 (en) 2010-11-12 2013-05-28 Bayer Cropscience Ag Process for the preparation of 2,2-difluoroethylamine starting from a benzylamine compound
WO2012062702A1 (fr) 2010-11-12 2012-05-18 Bayer Cropscience Ag Procédé de production de 2,2-difluoro-éthylamine à partir d'un composé benzylamine
WO2012062703A1 (fr) * 2010-11-12 2012-05-18 Bayer Cropscience Ag Procédé de production de 2,2-difluoro-éthylamine à partir de prop-2-èn-1-amine
US8586756B2 (en) 2010-11-12 2013-11-19 Bayer Cropscience Ag Process for the preparation of 2,2-difluoroethylamine derivatives starting from N-(2,2-difluoroethyl)prop-2-en-1-amine
CN103201251B (zh) * 2010-11-12 2015-12-02 拜耳知识产权有限责任公司 由苄胺化合物起始制备2,2-二氟乙胺的方法
CN103201251A (zh) * 2010-11-12 2013-07-10 拜耳知识产权有限责任公司 由苄胺化合物起始制备2,2-二氟乙胺的方法
JP2014501711A (ja) * 2010-11-12 2014-01-23 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー Ｎ−（２，２−ジフルオロエチル）プロパ−２−エン−１−アミンから出発して２，２−ジフルオロエチルアミン誘導体を調製する方法
CN103443067B (zh) * 2011-01-24 2015-04-22 拜耳知识产权有限责任公司 由2,2-二氟-1-氯乙烷起始制备2,2-二氟乙胺的方法
CN103443067A (zh) * 2011-01-24 2013-12-11 拜耳知识产权有限责任公司 由2,2-二氟-1-氯乙烷起始制备2,2-二氟乙胺的方法
US8580973B2 (en) 2011-01-24 2013-11-12 Bayer Cropscience Ag Process for the preparation of 2,2-difluoroethylamine
WO2012101044A1 (fr) * 2011-01-24 2012-08-02 Bayer Cropscience Ag Procédé de préparation de 2,2-difluoroéthylamine à partir de 2,2-difluoro-1-chloroéthane
WO2014001245A1 (fr) 2012-06-29 2014-01-03 Bayer Cropscience Ag Procédé de production de dérivés de 2,2-difluoroéthylamine par alkylation de 2,2-difluoroéthylamine
US9376389B2 (en) 2012-06-29 2016-06-28 Bayer Cropscience Ag Process for preparing 2,2-difluoroethylamine derivatives by alkylating 2,2-difluoroethylamine
US9890120B2 (en) 2014-03-21 2018-02-13 Bayer Cropscience Aktiengesellschaft Preparation of N-[(6-chloropyridin-3-yl)methyl]-2,2-difluoroethan-1-amine by alkylation of 2,2-difluoroethylamine

Also Published As

Publication number Publication date
CN101835754B (zh) 2012-08-29
EP2200984A1 (fr) 2010-06-30
EP2200984B1 (fr) 2013-12-18
TW200922910A (en) 2009-06-01
ES2445653T3 (es) 2014-03-04
MX2010002453A (es) 2010-05-20
EP2039684A1 (fr) 2009-03-25
BRPI0816868A2 (pt) 2015-03-17
US8324393B2 (en) 2012-12-04
US20100274021A1 (en) 2010-10-28
BRPI0816868A8 (pt) 2015-10-27
IL204000A (en) 2013-11-28
JP5295248B2 (ja) 2013-09-18
JP2010539202A (ja) 2010-12-16
BRPI0816868B1 (pt) 2016-05-17
KR101520337B1 (ko) 2015-05-14
CN101835754A (zh) 2010-09-15
KR20100072026A (ko) 2010-06-29
TWI402245B (zh) 2013-07-21
DK2200984T3 (en) 2014-03-17

Similar Documents

Publication Publication Date Title
EP2200984B1 (fr) Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'imines
EP2193128B1 (fr) Procédé de fabrication de 4-aminobut-2-énoïque
EP2582673B1 (fr) .procédé de préparation de dérivés de 2,2-difluoréthylamine par alkylation avec 2,2-difluoro-1-halogéno-éthanes
EP2212289B1 (fr) Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'amides
EP0385210B1 (fr) Amidification de pyridines
EP2408746B1 (fr) Procédé destiné à la fabrication de dérivés de 2,2-difluoréthylamine par hydrogénisation d'imine
EP2203410B1 (fr) Procédé de préparation de 4-aminobut-2-énolides
EP3577114B1 (fr) Procédé de fabrication de dérivés d'imidazopyridine halogénée
EP2638010B1 (fr) Procédé de production de dérivés de 2,2-difluoro-éthylamine à partir de n-(2,2-difluoro-éthyl)prop-2-èn-1-amine
EP2408765B1 (fr) Nouveau procédé de préparation de composés énaminocarbonylés
EP2516421B1 (fr) Nouveau procédé de fabrication de 4-aminobut-2-énolides à partir de 4-alkoxyfuran-2(5H)-one ou de 4-arylalkoxyfuran-2(5H)-one
EP2467374B1 (fr) Nouveau procédé de fabrication de 4-aminobut-2-énoïque
EP2408764B1 (fr) Nouveau procédé de fabrication de composés d'énaminocarbonyles

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880107472.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08801866

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008801866

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 204000

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: MX/A/2010/002453

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1519/DELNP/2010

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 12677951

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2010525231

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20107008224

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: PI0816868

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20100318